Given a function $f \colon \mathbb{R^n} \to E$, where $E$ is a locally convex Hausdorff TVS, we say that $f$ is differentiable at $x \in \mathbb{R^n}$ if there exists some $Df(x) \in \mathcal{L}(\mathbb R ^n, E)$ such that $$ f(x+h) = f(x) + Df(x)h + o(|h|). $$ Here $g = o(|h|)$ if $\lim_{h\to0} \frac{g(h)}{|h|} = 0$ as a limit in $E$.
Given such a function, we have for all $\psi \in E'$ that $$ \psi \circ f(x+h) = \psi \circ f(x) + \psi \circ Df(x)h + o(|h|). $$ (Note the slight abuse of little-o notation; the first one is $E$-valued while the second is $\mathbb{R}$-valued.) Since $\psi \circ Df(x) \in \mathcal{L}(\mathbb R ^n,\mathbb R)$, this means $\psi \circ f$ is differentiable in the classical sense.
Question 1: Does the reverse hold, i.e. if $\psi \circ f$ is diffentiable at $x$ for all $\psi \in E'$, is $f$ itself then differentiable at $x$? NO, see a nice counterexample given here.
Question 2: What if we look at differentiablility on an open $U$ instead of one point $x$?